Tristate electrochromic device

ABSTRACT

An electrochromic medium for use in a tristate electrochromic device, comprising: (a) at least one solvent; (b) at least one anodic material; (c) at least one cathodic material, wherein both of the anodic and cathodic materials are electroactive and at least one of the anodic and cathodic materials is electrochromic; (d) wherein, in a first state, the electrochromic medium exhibits a maximum light transmission; (e) wherein, in a second state, variable attenuation occurs to a significant extent in one of visible radiation or near-infrared radiation without significant attenuation in the other; and (f) wherein, in a third state, variable attenuation occurs to a significant extent in the other spectral region.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.10/850,989, filed on May 21, 2004, now U.S. Pat. No. 6,876,479, which ishereby incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates in general to electrochromic devices and,more particularly, to a tristate electrochromic device having anodicand/or cathodic materials which, upon application of different appliedpotentials, can selectively absorb predetermined wavelengths ofelectromagnetic radiation, including visible radiation (i.e. visiblelight ranging in wavelength from approximately 400 nanometers (nm) toapproximately 750 nm) and/or near-infrared radiation (i.e. heat rangingin wavelength from approximately 750 nm to approximately 2,400 nm) andvice versa—depending upon the device configuration.

2. Background Art

Electrochromic devices have been known in the art for several years.Furthermore, the utilization of a plurality of anodic and/or cathodicmaterials in the medium of an electrochromic device is well known. See,for example, U.S. Pat. No. 5,998,617 entitled “ElectrochromicCompounds,” U.S. Pat. No. 6,020,987 entitled “Electrochromic MediumCapable Of Producing A Pre-selected Color,” U.S. Pat. No. 6,037,471entitled “Electrochromic Compounds,” U.S. Pat. No. 6,141,137 entitled“Electrochromic Media For Producing A Pre-selected Color,” U.S. Pat. No.6,193,912 entitled “Near Infrared-Absorbing Electrochromic Compounds AndDevices Comprising Same,” and U.S. application Ser. No. 10/283,506entitled “Electrochromic Device Having An Electron Shuttle,” all ofwhich are hereby incorporated herein by reference in their entirety.

While the above-identified references disclose utilizing a plurality ofanodic and/or cathodic materials in the medium of an electrochromicdevice, to the best of Applicant's knowledge, they do not enable a userto selectively absorb light in the visible or near-infrared regionsimply by varying the applied potential. The inability to operate inthis manner has caused prior art devices to be limited in a number ofapplications.

For example, during hot summer days when the sun is well above thehorizon, it may be desirable for an electrochromic device tosubstantially absorb near-infrared radiation (i.e. heat) withoutsubstantially absorbing visible radiation so that an environment (i.e.room, building, etcetera) remains both temperate as well as sufficientlyilluminated. However, as the sun approaches the horizon during, forexample, periods generally after sunrise and/or before sunset, it may bedesirable for an electrochromic device to substantially absorb bothnear-infrared radiation (i.e. heat) as well as visible radiation (i.e.light), to, in turn, reduce glare and/or undesirable illuminationeffects associated with the same.

During winter days in cold climates it may be desirable to have a deviceabsorb only visible light during the coldest morning hours when the sunis low on the horizon and to allow the near-infrared light to enter andallow some solar warming of the interior of the building, while at thesame time reducing unwanted glare. When the sun is higher in the sky,the device could be turned off to allow both visible light andnear-infrared radiation to enter the building, thereby reducing the needfor artificial illumination and allowing for solar heat to enter thebuilding. Later in the afternoon, it may be desirable to block both thevisible and near-infrared radiation for thermal and visual comfort.

It has now been surprisingly discovered that selective utilization ofone or more anodic and/or cathodic electroactive materials enables anelectrochromic medium, and, in turn, an electrochromic device, tooperate between at least three regions or states (referred to as atristate device), namely (1) a first state (i.e. when a potentialdifference less than that sufficient to cause electrochemical oxidationor reduction of the anodic and cathodic materials is applied, a.k.a. theopen circuit state or high transmission state) wherein the device hasits maximum light transmission; (2) a second state (i.e. an appliedpotential between the minimum potential where oxidation or reduction ofthe anodic and cathodic materials occurs up to a “second” potentialdifference) wherein variable attenuation of either visible radiation ornear-infrared radiation occurs to a significant extent depending on thedevice configuration without significant attenuation in the otherspectral region; and (3) a third state (i.e. an applied potentialbetween the “second” potential and a “third” potential difference)wherein variable attenuation occurs to a significant extent in the otherspectral region depending on device configuration. It will be understoodthat attenuation refers to the relative change in transmission of adevice as the potential is changed.

It is therefore an object of the present invention to provide a tristateelectrochromic device that remedies the aforementioned limitationsassociated with conventional electrochromic devices.

SUMMARY OF THE INVENTION

The present invention is directed to an electrochromic medium for use ina tristate electrochromic device, comprising: (a) at least one solvent;(b) at least one anodic material; (c) at least one cathodic material,wherein both of the anodic and cathodic materials are electroactive andat least one of the anodic and cathodic materials is electrochromic; (d)wherein the medium has its maximum light transmission in a first state;(e) wherein the medium variably attenuates either visible radiation ornear-infrared radiation to a significant extent without significantattenuation in the other spectral region in a second state; and (f)wherein the medium variably attenuates radiation in the other spectralregion in a third state.

The present invention is also directed to a tristate electrochromicdevice, comprising: (a) a first substantially transparent substratehaving an electrically conductive material associated therewith; (b) asecond substrate having an electrically conductive material associatedtherewith; (c) an electrochromic medium contained within a chamberpositioned between the first and second substrates which comprises: (1)at least one solvent; (2) at least one anodic material; (3) at least onecathodic material, wherein both of the anodic and cathodic materials areelectroactive and at least one of the anodic and cathodic materials iselectrochromic; (d) wherein the tristate device has its maximum lighttransmission in a first state; (e) wherein the tristate device variablyattenuates either visible radiation or near-infrared radiation to asignificant extent without significant attenuation in the other spectralregion in a second state; and (f) wherein the tristate device variablyattenuates radiation in the other spectral region in a third state.

The present invention is further directed to an electrochromic devicecapable of operating between a first state, a second state, and a thirdstate, comprising: (a) a first substantially transparent substratehaving an electrically conductive material associated therewith; (b) asecond substrate having an electrically conductive material associatedtherewith; (c) an electrochromic medium contained within a chamberpositioned between the first and second substrates which comprises: (1)at least one solvent; (2) a first anodic material; (3) a first cathodicmaterial; (4) a second cathodic material, wherein both of the anodic andcathodic materials are electroactive and at least one of the anodic andcathodic materials is electrochromic; (d) wherein the anodic material ispresent “in excess” such that the current is limited by the firstcathodic material when the device reaches the high potential range ofthe second state and while operating in the second state only the firstcathodic material is reduced to a significant extent; and (e) whileoperating in the third state, the second cathodic material is reducedand when the high potential range of the third state is reached, thecurrent can be limited by either the anodic material or the combinationof cathodic materials (or balanced). The choice to limit current at theanode or the cathode can be made according to the teachings of U.S. Pat.No. 6,137,620, entitled “Electrochromic Media With ConcentrationEnhanced Stability, Process For The Preparation Thereof and Use InElectrochromic Devices” which contains a detailed description oflimiting current in an electrochromic device by selection ofconcentrations of the anodic and cathodic materials, and which is herebyincorporated herein by reference in its entirety.

In accordance with the present invention, an electrochromic device isprovided which is capable of operating between a first state, a secondstate, and a third state, comprising: (a) a first substantiallytransparent substrate having an electrically conductive materialassociated therewith; (b) a second substrate having an electricallyconductive material associated therewith; (c) an electrochromic mediumcontained within a chamber positioned between the first and secondsubstrates which comprises: (1) at least one solvent; (2) a firstcathodic material; (3) a first anodic material; (4) a second anodicmaterial, wherein both of the anodic and cathodic materials areelectroactive and at least one of the anodic and cathodic materials iselectrochromic; (d) wherein the cathodic material is present “in excess”such that the current is limited by the first anodic material when thedevice reaches the high potential range of the second state and whileoperating in the second state only the first anodic material is oxidizedto a significant extent; and (e) while operating in the third state, thesecond anodic material is oxidized and when the high potential range ofthe third state is reached, the current can be limited by either thecathodic materials or the combination of anodic material. It will beunderstood that the terms first and second anodic and cathodic materialmay include a single compound with multiple oxidation states that havesufficient stability in each of the oxidation states obtained duringoperation of the device for use in the same. It will be furtherunderstood that the second anodic or cathodic material could beprevented from being oxidized, in the case of an anodic material, orreduced, in the case of a cathodic material, by selecting materials withelectrochemical redox potentials that differ by a useful amount(typically more than 50 mV or more preferably by more than 100 mV) or byselecting materials displaying different electrode kinetics.

These and other objectives of the present invention will become apparentin light of the present specification, claims, and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to the drawingswherein:

FIG. 1 of the drawings is a cross-sectional schematic representation ofan electrochromic device fabricated in accordance with the presentinvention.

FIG. 2 of the drawings is a two-dimensional plot showing % transmissionas a function of applied potential for the medium of Experiment No. 1.

DETAILED DESCRIPTION OF THE INVENTION

Referring now to the drawings and to FIG. 1 in particular, across-sectional schematic representation of tristate electrochromicdevice 100 is shown, which generally comprises first substrate 112having front surface 112A and rear surface 112B, second substrate 114having front surface 114A and rear surface 114B, and chamber 116 forcontaining electrochromic medium 124. It will be understood thattristate electrochromic device 100 may comprise, for illustrativepurposes only, a window, a mirror, a display device, and the like. Itwill be further understood that FIG. 1 is merely a schematicrepresentation of tristate electrochromic device 100. As such, some ofthe components have been distorted from their actual scale for pictorialclarity. Indeed, numerous other electrochromic device configurations arecontemplated for use, including those disclosed in U.S. Pat. No.5,818,625 entitled “Electrochromic Rearview Mirror Incorporating A ThirdSurface Metal Reflector,” and U.S. Pat. No. 6,597,489 entitled“Electrode Design For Electrochromic Devices,” both of which are herebyincorporated herein by reference in their entirety.

First substrate 112 may be fabricated from any one of a number ofmaterials that are transparent or substantially transparent in thevisible region of the electromagnetic spectrum, such as, for example,borosilicate glass, soda lime glass, float glass, natural and syntheticpolymeric resins, plastics, and/or composites including Topas®, which iscommercially available from Ticona of Summit, N.J. First substrate 112is preferably fabricated from a sheet of glass having a thicknessranging from approximately 0.5 millimeters (mm) to approximately 12.7mm. Of course, the thickness of the substrate will depend largely uponthe particular application of the electrochromic device. Whileparticular substrate materials have been disclosed, for illustrativepurposes only, it will be understood that numerous other substratematerials are likewise contemplated for use—so long as the materials areat least substantially transparent and exhibit appropriate physicalproperties, such as strength, to be able to operate effectively inconditions of intended use. Indeed, electrochromic devices in accordancewith the present invention can be, during normal operation, exposed toextreme temperature variation as well as substantial UV radiation,emanating primarily from the sun.

Second substrate 114 may be fabricated from similar materials as that offirst substrate 112. However, if the electrochromic device is a mirroror comprises a mirrored surface, then the requisite of substantialtransparency is not necessary. As such, second substrate 114 may,alternatively, comprise polymers, metals, glass, and ceramics—to name afew. Second substrate 114 is preferably fabricated from a sheet of glasshaving a thickness ranging from approximately 0.5 mm to approximately12.7 mm. If first and second substrates 112 and 114, respectively, arefabricated from sheets of glass, then the glass can optionally betempered, heat strengthened, and/or chemically strengthened, prior to orsubsequent to being coated with layers of electrically conductivematerial (118 and 120).

One or more layers of electrically conductive material 118 areassociated with rear surface 112B of first substrate 112. These layersserve as an electrode for the electrochromic device. Electricallyconductive material 118 is desirably a material that: (a) issubstantially transparent in the visible region of the electromagneticspectrum; (b) bonds reasonably well to first substrate 112; (c)maintains this bond when associated with a sealing member; (d) isgenerally resistant to corrosion from materials contained within theelectrochromic device or the atmosphere; and (e) exhibits minimaldiffuse or specular reflectance as well as sufficient electricalconductance. It is contemplated that electrically conductive material118 may be fabricated from fluorine doped tin oxide (FTO), for exampleTEC glass, which is commercially available from Libbey Owens-Ford-Co.,of Toledo, Ohio, indium/tin oxide (ITO), doped zinc oxide or othermaterials known to those having ordinary skill in the art.

Electrically conductive material 120 is preferably associated with frontsurface 114A of second substrate 114, and is operatively bonded toelectrically conductive material 118 by sealing member 122. As can beseen in FIG. 1, once bonded, sealing member 122 and the juxtaposedportions of electrically conductive materials 118 and 120 serve todefine an inner peripheral geometry of chamber 116. Alternatively, edgesealing techniques may be utilized which are disclosed in U.S. PatentApplication Ser. No. 60/548,472 entitled “Vehicular Rearview MirrorElements and Assemblies Incorporating These Elements,” filed on Feb. 27,2004, which is hereby incorporated herein by reference in its entirety.

Electrically conductive material 120 may vary depending upon theintended use of the electrochromic device. For example, if theelectrochromic device is a mirror, then the material may comprise atransparent conductive coating similar to electrically conductivematerial 118 (in which case a reflector is associated with rear surface114B of second substrate 114). Alternatively, electrically conductivematerial 120 may comprise a layer of reflective material in accordancewith the teachings of previously referenced and incorporated U.S. Pat.No. 5,818,625. In this case, electrically conductive material 120 isassociated with front surface 114A of second substrate 114. Typicalcoatings for this type of reflector include chromium, rhodium,ruthenium, silver, silver alloys, and combinations thereof.

Sealing member 122 may comprise any material that is capable of beingadhesively bonded to the electrically conductive materials 118 and 120to, in turn, seal chamber 116 so that electrochromic medium 124 does notinadvertently leak out of the chamber. As is shown in dashed lines inFIG. 1, it is also contemplated that the sealing member extend all theway to rear surface 112B and front surface 114A of their respectivesubstrates. In such an embodiment, the layers of electrically conductivematerial 118 and 120 may be partially removed where the sealing member122 is positioned. If electrically conductive materials 118 and 120 arenot associated with their respective substrates, then sealing member 122preferably bonds well to glass. It will be understood that sealingmember 122 can be fabricated from any one of a number of materialsincluding, for example, those disclosed in: U.S. Pat. No. 4,297,401entitled “Liquid Crystal Display And Photopolymerizable SealantTherefor,” U.S. Pat. No. 4,418,102 entitled “Liquid Crystal DisplaysHaving Improved Hermetic Seal,” U.S. Pat. No. 4,695,490 entitled “SealFor Liquid Crystal Display,” U.S. Pat. No. 5,596,023 entitled “SealingMaterial For Liquid Crystal Display Panel, And Liquid Crystal DisplayPanel Using It,” U.S. Pat. No. 5,596,024 entitled “Sealing CompositionFor Liquid Crystal,” and U.S. Pat. No. 6,157,480 entitled “Seal ForElectrochromic Devices,” all of which are hereby incorporated herein byreference in their entirety.

For purposes of the present disclosure, and as will be explained ingreater detail herein below, electrochromic medium 124 comprises atleast one solvent, at least one anodic material, and at least onecathodic material, wherein the one or more anodic and cathodic materialsare selectively chosen so that electrochromic device 100 is capable ofoperating among a first state, a second state, and a third state.

Electrochromic medium 124 is preferably chosen from one of the followingcategories:

(1) Single-layer, single-phase—The electrochromic medium may comprise asingle-layer of material which may include small non-homogenous regionsand includes solution-phase devices where a material may be contained insolution in the ionically conducting electrolyte which remains insolution in the electrolyte when electrochemically oxidized or reduced.Solution phase electroactive materials may be contained in thecontinuous solution-phase of a gel medium in accordance with theteachings of U.S. Pat. No. 5,928,572 entitled “Electrochromic Layer AndDevices Comprising Same,” and International Patent Application SerialNo. PCT/US98/05570 entitled “Electrochromic Polymeric Solid Films,Manufacturing Electrochromic Devices Using Such Solid Films, AndProcesses For Making Such Solid Films And Devices,” both of which arehereby incorporated herein by reference in their entirety.

More than one anodic and cathodic material can be combined to give apre-selected color as described in: U.S. Pat. No. 5,998,617 entitled“Electrochromic Compounds,” U.S. Pat. No. 6,020,987 entitled“Electrochromic Medium Capable Of Producing A Pre-selected Color,” U.S.Pat. No. 6,037,471 entitled “Electrochromic Compounds,” and U.S. Pat.No. 6,141,137 entitled “Electrochromic Media For Producing APre-selected Color,” all of which were previously incorporated herein byreference in their entirety.

The anodic and cathodic materials may also be combined or linked by abridging unit as described in U.S. Pat. No. 6,241,916 entitled“Electrochromic System” and/or U.S. Patent Publication No. 2002/00152214A1 entitled “Electrochromic Device,” which are hereby incorporatedherein by reference in their entirety. The electrochromic materials mayalso include near-infrared (NIR) absorbing compounds as described inU.S. Pat. No. 6,193,912 entitled “Near Infrared-Absorbing ElectrochromicCompounds And Devices Comprising Same,” which was previouslyincorporated herein by reference in its entirety.

It is also possible to link anodic materials or cathodic materials bysimilar methods. The concepts described in these patents can further becombined to yield a variety of electroactive materials that are linkedor coupled, including linking of a redox buffer such as linking of acolor-stabilizing moiety to an anodic and/or cathodic material.

The anodic and cathodic electrochromic materials can also includecoupled materials as described in U.S. Pat. No. 6,249,369 entitled“Coupled Electrochromic Compounds With Photostable Dication OxidationStates,” which is hereby incorporated herein by reference in itsentirety.

The concentration of the electrochromic materials can be selected astaught in U.S. Pat. No. 6,137,620 entitled “Electrochromic Media WithConcentration Enhanced Stability, Process For The Preparation Thereofand Use In Electrochromic Devices,” the entirety of which has beenpreviously incorporated herein by reference.

Additionally, a single-layer, single-phase medium may include a mediumwhere the anodic and cathodic materials are incorporated into a polymermatrix as is described in International Application Serial No.PCT/WO99/02621 entitled “Electrochromic Polymer System,” which is herebyincorporated herein by reference in its entirety, and InternationalPatent Application Serial No. PCT/US98/05570 entitled “ElectrochromicPolymeric Solid Films, Manufacturing Electrochromic Devices Using SuchSolid Films, And Processes For Making Such Solid Films And Devices.”

(2) Multi-layer—The medium may be made up in layers and includes amaterial attached directly to an electrically conducting electrode orconfined in close proximity thereto which remains attached or confinedwhen electrochemically oxidized or reduced.

(3) Multi-phase—One or more materials in the medium undergoes a changein phase during the operation of the device, for example a materialcontained in solution in the ionically conducting electrolyte forms alayer on the electrically conducting electrode when electrochemicallyoxidized or reduced.

In addition, electrochromic medium 124 may comprise other materials,such as light absorbers, light stabilizers, thermal stabilizers,antioxidants, thickeners, viscosity modifiers, tint providing agents,redox buffers, and mixtures thereof. Suitable UV-stabilizers mayinclude: the material 2-ethyl-2-cyano-3,3-diphenyl acrylate, sold byBASF of Parsippany, N.Y., under the trademark Uvinul N-35 and by AcetoCorp., of Flushing, N.Y., under the trademark Viosorb 910; the material(2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, sold by BASF under thetrademark Uvinul N-539; the material2-(2′-hydroxy-4′-methylphenyl)benzotriazole, sold by Ciba-Geigy Corp.under the trademark Tinuvin P; the material3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionicacid pentyl ester prepared from Tinuvin 213, sold by Ciba-Geigy Corp.,via conventional hydrolysis followed by conventional esterification(hereinafter “Tinuvin PE”); the material 2,4-dihydroxybenzophenone soldby, among many others, Aldrich Chemical Co.; the material2-hydroxy-4-methoxybenzophenone sold by American Cyanamid under thetrademark Cyasorb UV 9; and the material 2-ethyl-2′-ethoxyalanilide soldby Sandoz Color & Chemicals under the trademark Sanduvor VSU—to name afew.

For purposes of the present invention, anodic materials may include anyone of a number of materials including ferrocene, substitutedferrocenes, substituted ferrocenyl salts, substituted phenazines,phenothiazine, substituted phenothiazines including substituteddithiazines, thianthrene, substituted thianthrenes. Examples of anodicmaterials may include di-tert-butyl-diethylferrocene,5,10-dimethyl-5,10-dihydrophenazine (DMP),3,7,10-trimethylphenothiazine, 2,3,7,8-tetramethoxy-thianthrene,10-methylphenothiazine, tetramethylphenazine (TMP)— see U.S. Pat. No.6,242,602 B1 for synthesis, which is hereby incorporated herein byreference in its entirety, andbis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT)—seesynthesis of3,10-dimethoxy-7,14-(triethylammoniumbutyl)triphenodithazinebis(tetrafluoroborate) in U.S. Pat. No. 6,710,906 B2, which is herebyincorporated herein by reference in its entirety. It is alsocontemplated that the anodic material may comprise a polymer film, suchas polyaniline, polythiophenes, polymeric metallocenes, or a solidtransition metal oxide, including, but not limited to, oxides ofvanadium, nickel, iridium, as well as numerous heterocyclic compounds,etcetera. It will be understood that numerous other anodic materials arecontemplated for use including those disclosed in U.S. Pat. No.4,902,108 entitled “Single-Compartment, Self-Erasing, Solution-PhaseElectrochromic Devices, Solutions For Use Therein, And Uses Thereof,” aswell as U.S. Pat. No. 6,188,505 B1 entitled “Color-StabilizedElectrochromic Devices,” and U.S. patent application Ser. No. 10/054,108entitled “Controlled Diffusion Coefficient Electrochromic Materials ForUse In Electrochromic Mediums And Associated Electrochromic Devices,”all of which are hereby incorporated herein by reference in theirentirety.

Cathodic materials may include, for example, viologens, such as methylviologen tetrafluoroborate, octyl viologen tetrafluoroborate(octylviologen), or benzyl viologen tetrafluoroborate, ferrociniumsalts, such as (6-(tri-tert-butylferrocinium)hexyl)triethylammoniumdi-tetrafluoroborate (TTBFc⁺)—see U.S. patent application Ser. No.10/681,538 entitled “Reversible Electrodeposition Devices And AssociatedElectrochemical Media” for synthesis which is hereby incorporated hereinby reference in its entirety. It will be understood that the preparationand/or commercial availability for each of the above-identified cathodicmaterials is well known in the art. See, for example, “The BipyridiniumHerbicides” by L. A. Summers (Academic Press 1980). While specificcathodic materials have been provided for illustrative purposes only,numerous other conventional cathodic materials are likewise contemplatedfor use including, but by no means limited to, those disclosed inpreviously referenced and incorporated U.S. Pat. No. 4,902,108, U.S.Pat. No. 6,188,505, and U.S. patent application Ser. No. 10/054,108entitled “Controlled Diffusion Coefficient Electrochromic Materials ForUse In Electrochromic Mediums And Associated Electrochromic Devices.”Moreover, it is contemplated that the cathodic material may comprise apolymer film, such as various substituted polythiophenes, polymericviologens, an inorganic film, or a solid transition metal oxide,including, but not limited to, tungsten oxide.

For illustrative purposes only, the concentration of the anodic andcathodic materials can range from approximately 1 millimolar (mM) toapproximately 500 mM and more preferably from approximately 2 mM toapproximately 100 mM. While particular concentrations of the anodic aswell as cathodic materials have been provided, it will be understoodthat the desired concentration may vary greatly depending upon thegeometric configuration of the chamber containing electrochromic medium124.

For purposes of the present disclosure, a solvent of electrochromicmedium 124 may comprise any one of a number of common, commerciallyavailable solvents including 3-methylsulfolane, dimethyl sulfoxide,dimethyl formamide, tetraglyme and other polyethers; alcohols such asethoxyethanol; nitrites, such as acetonitrile, glutaronitrile,3-hydroxypropionitrile, and 2-methylglutaronitrile; ketones including2-acetylbutyrolactone, and cyclopentanone; cyclic esters includingbeta-propiolactone, gamma-butyrolactone, and gamma-valerolactone;propylene carbonate (PC), ethylene carbonate; and homogenous mixtures ofthe same. While specific solvents have been disclosed as beingassociated with the electrochromic medium, numerous other solvents thatwould be known to those having ordinary skill in the art having thepresent disclosure before them are likewise contemplated for use.

In one embodiment of the present invention, electrochromic medium 124 oftristate electrochromic device 100 comprises: a first anodic material(A₁); a first cathodic material (C₁); and a second cathodic material(C₂), which in a first state (i.e. the open circuit, zero potential, orhigh transmission state) substantially absorbs neither visible radiationnor near-infrared radiation.

During operation of the device in the second state (the potential rangeof which is determined by the anodic and cathodic materials selected foruse in the device), the anodic material is oxidized from (A₁) to (A₁ ⁺),and the current is limited by the first cathodic material (C₁) beingreduced to (C₁ ⁻). In this second state one region of theelectromagmetic spectrum, either the visible or the near-infrared, isabsorbed without substantial change in the absorbance in the otherregion. If the absorbance takes place in the near-infrared then such astate, as previously discussed, is ideal for maintaining a temperateenvironment in a building, room and/or office during hot summer dayswithout substantially absorbing visible illumination from the sun.

During operation of the device in the third state (the potential rangeof which is determined by the anodic and cathodic materials selected foruse in the device), the remainder of the first anodic material isoxidized from (A₁) to (A₁ ⁺), and the current is limited by the secondcathodic material being reduced from (C₂) to (C₂ ⁻). In this third statea substantial portion of both near-infrared and visible radiation isabsorbed. Such a state, as previously discussed, is ideal formaintaining a temperate environment and reducing glare and/orundesirable illumination effects associated with periods generally aftersunrise and/or before sunset—when the sun approaches the horizon.

In another embodiment of the present invention, electrochromic medium124 of tristate electrochromic device 100 comprises: a first cathodicmaterial (C₁); a first anodic material (A₁); and a second anodicmaterial (A₂), which in a first state substantially absorbs neithervisible radiation nor near-infrared radiation.

During operation of the device in the second state (the potential rangeof which is determined by the anodic and cathodic materials selected foruse in the device), the cathodic material is reduced from (C₁) to (C₁⁻), and the current is limited by the first anodic material (A₁) beingoxidized to (A₁ ⁺). If the absorbance takes place in the visible regionthen such a state, as previously discussed, is ideal for promotingvisual comfort as well as a temperate environment, during, for example,cold winter days.

During operation of the device in the third state (the potential rangeof which is determined by the anodic and cathodic materials selected foruse in the device), the remainder of the cathodic material is reducedfrom (C₁) to (C₁ ⁻), and current is limited by the second anodicmaterial being oxidized from (A₂) to (A₂ ⁺). In this third state asubstantial portion of both near-infrared and visible radiation isabsorbed. Such a state, as previously discussed, is ideal formaintaining a temperate environment and reducing glare and/orundesirable illumination effects associated with periods generally aftersunrise and/or before sunset—when the sun approaches the horizon.

Tristate electrochromic devices can be used in a wide variety ofapplications wherein the transmitted or reflected light/heat can bemodulated. Such devices include mirrors; windows for the exterior of abuilding, home or vehicle; skylights for buildings including tubularlight filters; windows in office or room partitions; and light filtersfor photographic devices and light sensors.

The electrochromic media of the present invention utilize many differentmaterials, the preparation and/or commercially available sources areprovided herein, unless the material is well known in the art. It willbe understood that, unless specified otherwise, the starting reagentsare commercially available from Aldrich Chemical Co., of Milwaukee,Wis., Ciba-Geigy Corp., and/or other common chemical suppliers. It willbe further understood that conventional chemical abbreviations will beused when appropriate including the following: grams (g); milliliters(mL); moles (mol); millimoles (mmol); molar (M); millimolar (mM); poundsper square inch (psi); hours (h); and degrees Centigrade (° C.).

In support of the present invention, multiple experiments were conductedwherein tristate devices were prepared and their functionality wasvalidated.

It will be understood that in each of the experiments provided below,the electrochromic medium materials were dissolved in propylenecarbonate (PC).

Experiment No. 1

In this experiment the electrochromic medium was prepared by mixing thefollowing materials together in the concentrations provided below:

Experiment No. 1 Component Material Concentration First Anodic DMP 10 mMSecond Anodic TPDT 30 mM First Cathodic Octylviologen 55 mM TintingAdditive TMP  4 mM

The medium of Experiment No. 1 was associated with an electrochromicwindow for testing. It will be understood that an amount of TMP wasadded to the electrochromic medium to intentionally produce a lightlytinted or “grey” colored medium. Specifically, the window comprised two2×5 inch glass substrates. Surface (112B) of the first substrate (112)was coated with generally clear, conductive indium/tin oxide (ITO), andthe second substrate (114) was coated with indium/tin oxide (ITO) onsurface (114A). The substrates were spaced 137 microns apart foraccommodating the medium. The window was filled with theabove-identified medium via conventional vacuum backfilling. Afterfabrication, the absorbance of the device was measured at voltagesranging from between 0.0 V and 1.4 V using conventional spectroscopy.Spectral data relative to Experiment No. 1 is provided herein below.

% of Applied Total Solar % of Solar Radiation % of Solar RadiationPotential Radiation Transmitted in the Transmitted in the (V)Transmitted NIR Region Visible Region 0.0 61.8 49.3 72.6 0.1 61.8 49.372.6 0.2 63.2 50.5 74.3 0.3 62.5 50.5 72.9 0.4 58.5 50.4 65.7 0.5 50.750.0 51.6 0.6 40.1 48.9 32.9 0.8 27.6 44.6 13.3 0.9 26.5 43.7 12.0 1.023.4 39.7 9.7 1.1 17.6 30.0 7.1 1.2 17.6 30.0 7.1 1.4 14.4 24.6 5.9

It can been seen numerically in the table above, or graphically in FIG.2, that through the second state (approximately 0.1 V—approximately 0.9V for this particular device) the visible radiation transmitted isreduced by a factor of about 6 while the NIR radiation transmittedremains largely unchanged, and that through the third state(approximately 0.9 V—approximately 1.4 V for this particular) the NIRlight transmitted is reduced to roughly 50% of the value at the end ofthe second state and radiation in the visible is reduced by about 50%.

While in the examples anodic near-infrared absorbers have been used, itis also contemplated that cathodic materials with near-infraredabsorbance be utilized in devices of the present invention.

Experiment No. 2

In this experiment the electrochromic medium was prepared by mixing thefollowing materials together in the concentrations provided below:

Experiment No. 2 Component Material Concentration First Cathodic TTBFc⁺12 mM Second Cathodic Octylviologen 30 mM First Anodic TPDT 60 mM

The medium of Experiment No. 2 was associated with an electrochromicwindow for testing. Specifically, the window comprised two 2×5 inchglass substrates. Surface (112B) of the first substrate (112) was coatedwith generally clear, conductive indium/tin oxide (ITO), and the secondsubstrate (114) was coated with indium/tin oxide (ITO) on surface(114A). The substrates were spaced 137 microns apart for accommodatingthe medium. The window was filled with the above-identified medium viaconventional vacuum backfilling. After fabrication, the absorbance ofthe device was measured at voltages ranging from between 0.0 V and 1.2 Vusing conventional spectroscopy. Spectral data relative to ExperimentNo. 2 is provided herein below.

% of Applied Total Solar % of Solar Radiation % of Solar RadiationPotential Radiation Transmitted in the Transmitted in the (V)Transmitted NIR Region Visible Region 0.0 58.2 46.1 68.7 0.9 33.1 20.444.2 1.2 12.5 10.6 14.2

It can been seen that through the second state the NIR radiationtransmitted is reduced by more than 50% while the visible radiationtransmitted remains at 66% its original level, and that through thethird state the visible light transmitted is reduced to roughly 25% ofthe value at the end of the second state and radiation in the NIR isreduced by less than 50%.

While the invention has been described in detail herein in accordancewith certain preferred embodiments thereof, many modifications andchanges therein may be effected by those skilled in the art.Accordingly, it is our intent to be limited only by the scope of theappending claims and not by way of details and instrumentalitiesdescribing the embodiments shown herein.

1. An electrochromic medium, comprising: at least one solvent; at leastone anodic material; at least one cathodic material; wherein, in a firststate, the electrochromic medium exhibits a transmission in the visibleradiation spectral region and the near-infrared radiation spectralregion; wherein, in a second state, the electrochromic medium exhibits alower transmission than the transmission in the first state in one ofthe visible radiation spectral region or the near-infrared radiationspectral region without material attenuation in the other spectralregion, and wherein, in a third state, the electrochromic mediumexhibits a lower transmission than the transmission in the first statein the other spectral region where the material attenuation did notoccur in the second state.
 2. The electrochromic medium according toclaim 1, wherein a first cathodic material comprises a ferrociniumspecies.
 3. The electrochromic medium according to claim 1, wherein asecond cathodic material comprises a viologen.
 4. The electrochromicmedium according to claim 1, wherein a first anodic material comprises adithiazine.
 5. The electrochromic medium according to claim 1, wherein afirst cathodic material comprises a ferrocinium species, a secondcathodic material comprises a viologen, and a first anodic materialcomprises a dithiazine.
 6. The electrochromic medium according to claim5, wherein the concentration of the first cathodic material ranges fromapproximately 1 mM to approximately 500 mM, wherein the concentration ofthe second cathodic material ranges from approximately 1 mM toapproximately 500 mM, and wherein the concentration of the first anodicmaterial ranges from approximately 1 mM to approximately 500 mM.
 7. Theelectrochromic medium according to claim 6, wherein the electrochromicmedium further comprises at least one of a cross-linked polymer matrix,a free-standing gel, and a substantially non-weeping gel.
 8. Theelectrochromic medium according to claim 1, wherein a first cathodicmaterial comprises a viologen.
 9. The electrochromic medium according toclaim 1, wherein a first anodic material comprises a substitutedphenazine.
 10. The electrochromic medium according to claim 1, wherein asecond anodic material comprises a dithiazine.
 11. The electrochromicmedium according to claim 1, wherein a first anodic material comprises asubstituted phenazine, a second anodic material comprises a dithiazine,and a first cathodic material comprises a viologen.
 12. Theelectrochromic medium according to claim 11, wherein the concentrationof the first anodic material ranges from approximately 1 mM toapproximately 500 mM, wherein the concentration of the second anodicmaterial ranges from approximately 1 mM to approximately 500 mM, whereinthe concentration of the first cathodic material ranges fromapproximately 1 mM to approximately 500 mM.
 13. The electrochromicmedium according to claim 12, wherein the electrochromic medium furthercomprises at least one of a cross-linked polymer matrix, a free-standinggel, and a substantially non-weeping gel.
 14. An electrochromic device,comprising: at least one substrate having an electrically conductivematerial associated therewith; and the electrochromic medium accordingto claim
 1. 15. The electrochromic device according to claim 14, whereinthe device comprises an electrochromic window.
 16. The electrochromicdevice according to claim 14, wherein a substrate is coated with areflective material.
 17. The electrochromic device according to claim16, wherein the device comprises an electrochromic mirror.
 18. Anelectrochromic device, comprising: at least one substantiallytransparent substrate having an electrically conductive materialassociated therewith; an electrochromic medium which comprises: at leastone solvent; at least one anodic material; at least one cathodicmaterial; wherein, in a first state, the electrochromic medium exhibitsa transmission in the visible radiation spectral region and thenear-infrared radiation spectral region; wherein, in a second state, theelectrochromic medium exhibits a lower transmission than thetransmission in the first state in one of the visible radiation spectralregion or the near-infrared radiation spectral region without materialattenuation in the other spectral region, and wherein, in a third state,the electrochromic medium exhibits a lower transmission than thetransmission in the first state in the other spectral region where thematerial attenuation did not occur in the second state.